Process of converting oils



Nov. 23 1926.

. G. l..i ERICHARD Er AL Pnocss oF CONVERTING ons Filed May e, 1922 method of heating higlhaluminum chlorid for t- Paienie'a Nov. 23,1926.

erronea I.. Pmcnann aan mi sIoNons To eurinnsrmmc conny,

roRArIoN or Texas.'

anrlnannnnsoa, or roaranrn'un, rms, As-- orfrmsnunon, raNNsYLvam, a conrnocass or coiivnn'rnie oIL's.

Application led `lay 8, 41922. Serial No. 558,888#l This invention vrelates to .converting oils 4with aluminum chloridiand it comprises a boiling oils with e production of va- ,pors of lower boiling'oilswherein the heat necessaryy for lmaintaining the temperature of thesystem. and for producing such va- 1pors is -furnished by circulating'fluids in eat-transferring relationship thereto; all as more `fully hereinafter set forth and as A claimed.

As is now known, itis feasible to utilize the catalyticy powersv of anhydrous alumimlm chlorid in the conversion f'high boil'- ing petroleum oils intov lower boiling oils;A as in manufacturing gasolinerfrom gas oil,

etc. In theordinary or cracking distillation -of a gasv oil lhaving 600F., the .temperature steadily rises wit production of gas and coke and a comparatively small'yield ofunsaturated, low grade gasoline and keroseneb By admixing such a j ywith av portion to form a heavy Soluble in the ou. n y y amount of ,chloridsayy the 5 per cent mengas oi-l however witlranhydrous aluminum chlorid in small amount, say, 5

heating, free ebullition takes p` ace atabout 475 and rises but slowly to 450G-550; 'the cbullition producinglarge yields of the. vapors of clean, saturatedI gasoline, or of gasoline and kerosene, as the case may be. The y distillate may be gasoline with .an endboiling .point of'sa'y, 300. F.;a boilin -point mucli below the temperature at whichethe gasoline is formed. f

,i The aluminum vchloiid'is not indefinitely On additionof a small tioned, to hot oil, it unites or melts -down oily liquid In tending to underlie the rest of the oil.

fpractice, in order to zet large area contact between the `two liquids .and for other rea- I sonsvigorous agitation is employed; the efi fort being to keep the' aluminumvchlorid in As thc catalyzing action goes on,

suspension oremulsiiied as much as may be.` the oily liquid gradually loses its original highl activityi'and becomes thicker in consistency.v

y In the end, it may become asplialtic or even coky. At such a time as the judgment of the voperator may deem expedient, the spent aluminum chlorid is allowed to settle outy andgis removed and sent to a recoveryfplant vtore'gfaiu aluminum chlorid iu its original highly active form.

a boiling point of, sager cent, and- Looked /at in one way, the `operation is that ,of vaporization' of the K oil (as gasoline) and in volatilizing'i consumption of heat is considerable; The necessity for large ,amountsof heat is increased by the common practice of using air cooled reflux'condensers to condense and return vapors of'aluminum chl rid,vetc.l All' the heat .dissipated by-tlieaircooled refluxf con'densers mustbe again supplied` to the system.' Ordinarily',

the stills in which the actions the operation is performed are heated in the in` some soit of furnace chamben. This usualway, at their bases; thestill being set brings several mechanical diiliculties withit.

For one thing, the; heavyjaluminum .chlorid compound tends to settle to the bottom and bake on the heating-'elements with a rapid lossl in activity. acts, more or less, to-slow the transmission of heat. For this reason (and-also" because of the relatively great amount of heat which must vbe furnished through a relatively smalll area of metal, the still walls are neces- Also, the baked-on layerl sarily k'ept at a temperature much above that which is In the stated example, and aluminumchlorid may y reach' a heat-above say 550 F. but the heated walls ofthe still must be kept much vabove this temperature; being, so -to speak, super heated. `The net result is a'wast'e of' heat and unduly early deterioration' ofsome or milch of the aluminum chlorid. That chlo necessary to maintain the reaction.

rid which comes into 'contact with,'or bakes on the walls, is apt to be subjected to temperatures very much above the reaction temperature of 50G-550; The' oil in contact with the walls is also=morefor less-cracked; a result not here desired@v In the presentinvention, we obviate the 'noted difficulties and secure a number of new advfantages by the expedient of delivering hea much above that required' for the reaction and production of free ebullition. We maintain a heating surface of large area at a rela'- tively low ltemperature* instead of a small .surfacev at a high temperature and thereby secure av longer period ofactivity-'foig-pur aluminum chloi'id. vIn Wer-ff i vto the system at a temperature not' lace,k

the-bathof gas oill not' at any timey ics within thcbody' of oilfpaudalumin'um nch ori'd 1 a coil system and through vthe coil.y system wc send a rapid current of heating fluid (oil or oil vapor) usually at ottempera-attire only .a few'deg'rees above that necessary for reaction with the particular oil under dis tillation'; the, excess 'in' temperature Y bein'gfl merely that necessaryl to give "'@goodf heat transmission through the metal wall of the tubing. In so doing, there is no opportunity for either the aluminum chlorid or the 'oil .f to ,become over-heated; and a given charge of aluminum chlo'rid is much more long' lived, with aconsequent ycheapeiiingin `the whole" operation; yanhydrous aluminum chlorid"',being a' relatively expensive ,clieniical.

In the accompanying drawings ,weA have shown )more or less diagrainniatically, `one forni of apparatus useful in'vthe lpffartorniance ofyourfplrocess. l l i, i

The'view yis in longitudinal section, a part beingin elevation. l j -Refer'ringto thedrawiiigs liiidioates a furnace inw'hicli is lmounted atubular heater comprising an 'upper druni'Q and lower drum 3 connected by the tubesy 4.2 The fiir-f..

nace isprovided with the tire. box 5 and oil or gas burner 6, The baille? causesy and production of gases and vapors from ythe Oil. The oil"heated in this preliniinary heater may bel admitted to they lower druui through valve inlet lO'andniay be circulated by means of the pump 11 through the coil 12 located in'tliecmiverter or reaction chamber y13; the oil` in this ease circulating downwardly 'through'- the lieatingelenients and upwardly' through ihe coils in theconverter. The circulation ofthe hot oil may be. either'iiou'i. the lower drum 3 upwardly as shown byth'e full line arrows to the hottorn of the 4coil 19 as justdesci'ihed or it may be iii the opposite direction as is shown by the dotted arrows'ti'oin the upper drinn 2 tothe top of the coill l2, the valves on the lines being' adjusted in accordance with the circulation desired. AssumingA the circulation is upward in the coil 12in the converter 13, the oil passes from pump 11 by line 14 through the coil and thence out by liues15 and v1G to the' expansion chamber 17, liquid oil being returnfldthrough line 18 andliine lil-to the' upper` drum 2. Any Vapois, as of cracked products, given off by the oil in heating, are released in, this expansion chamber.` If the circulation is in the oppositeidirectielidthe oil leaves y drinn "2 through valved line 19, the valves on lines '16 and 18 being,closedanihthe valve 19 on theliiie 19d'op`ened, and lenterethe coil. 12 atthe upper part throughlline 15, leaving the.

ing suitably regulated. It vapor heating isA desired this iii-ay be secured hy charging theE y y heater syslen'i either with low boilingl'oil. such as naphtha, or with a high boiling oil,

the heat maintained`aiouiid"t'ubes @being then great enough to' pr duce'craeking or' destructive distillation. In either event,y

vapors (or rvaporsland gas) leave by the Vheater pipe ltland pass tliropiigifli.coil`12l in ya downward direction, condensate being withdrawn by valved pipe 18() and sent to a suitableyplace of disposition (notshown)'.,V

iUneondeiised vaporsjand gases passupward through 18 to the. 'chamber '17." If more vapor or vapor and gas is being produced `than required in the heatingv coil,the eX-` cess may pass through pipe'lt intothe rei i leaiffiiig chamber 17.

.'lhe'coi'iverter is providedwi'th ya lconical shaped bottom 21 having the Talved drawolt foral'unnni'im cl-ilorid's'ludge and 1s further provided' with'y inlets 23jand 2l for high boiling oil to'be converted iiit'o lower boiling' oils and for aluminum chlorid. The latter may he introduced in the formot' a mixture of aluminum chloridand oil. The

converter is It'urth'er vprovided with interior,

`sli-eve. 25 mounted on` the spider armsl26 'v1 and having' the' propeller 27 at the'bottom' tliercoi" operated by the -:sh/aft 2l) and thepim ion 3() lading to a "motor (not shownh The propeller operates to circulate vthe e'on- ,Y y tents ot the converter upwardly in' the sleeve and downwardly b'etweenrthe sleeve and the interior walls of thev converter. The confrertcigis equipped with the' preliminary air cooled eonilenser il having' Vapor'linc 3 2 loading to a second air cooled condenser 335" V such second air cooled condenser-'being -pro=- vided with a back trap'line 34 having a seal.'

,35. The first air cooled condenser 31vm'ay he provided within thermometer 36 andthe second air cooled condenser may he provided .Y with thermometer 37 for observation of teni perature. 'Usually the process isirun in such a way that the, vapors, goingl to exit' at the top of the second air cooled condenser 33 do not leave thesystem at more than y350 F.`

Aluminum chlorid, or aluminum ehlorid compounds,`- and heavy oils .condensed in the reiux condensers leave 33 through 34 for return to the converter. Condensiite from 31 returns tohthe converter through 38. -Vapers leave the'second condenser by vapo line 39 and go to the final condenser coil 40 in'tlie condenser box 50. from which the pass the gas trap 5l and go to the stock tan t (not shown) by line 52.

vI'leferring to the expansion chamber 17 which serves for the separation of liquid oil from vapors or vapors and gases, the oil can'tlow back to either drum`2or 3 in accordanceI with the circulation established, while vapors may pass lby line 53 toan air cooled condenser 54. Condensates therefrom vmay be sent into the converter line 55,1if l ,teniperature of thebath of aluminm chlorid 'and oi-l is set and maintained, the co1iSump-. tion of lient by increased `ebullition tending desired, the valves being regulated accordingly. Where oil isintroduced into the' converter from this source, ,the supply' of .oil' at'- 10 may be 4correspondingly increased.

l The vapors" from condenser 54er the vapors directlv taken from 'expansion .chamber 17,-

depending upon the operation selected, nia-y pass throuf'vh 1ine156,fvalve 57 thereon being openet'to l the condensing-coil 58 lov to a stocktankf (not shown). lhe .valve ing oil'fand aluminumch oridpfrom the con.-

Mbaiis and sin@ these pensif obtained by cracking ,may lcontain 'unsaturated bodies, f aluminum .chlorid will take upjthe unsatudenser. Since aluminum chlorid preferen-- tially combines with unsaturated hydrocarrated bodiesiand return with the'm Ato -the r rated gasoline vapors pjiss'inlg. forward vapors coiningyfrom' thefeonverter.

through/32 v`andf39 may creased. ".Anlyzincondensed vaporsv of light somewhat insaturatedggyg forward "1hr/ with'tiut mim-'Wille .va rs 'fram *be expansin' chamber 17 or tie air cooled -condgngergm 'T The process may' be operat d tothe airlcooled condenser 31, these vapors goingdirectlyto ythe lsecond coil 58 inthe condenser.f lox.v 'y Asf-isjiobvous from the descriptiomtlie k' describednpparatus n'iav` be lused in a` number of dixtercntjwaysf 'If a gas oil or solai' passes-.through coil 12 in cyclic flow. Eitpansio'n `'chaniber'l' then delivers very little vaporfto Q3. With any of these oils.- however, the tem ieratiircs in the tubular'heater4 may be raise. considerabl enough to forni a substantial volume o. cracked vapors.

H flhe light. products are then taken caregof in expansion chamber 17. The vapors may =go directly' to condensation through line 56 ;v

or they-may liep'artially fractionated in air cooled condenser 5ft' with return' of heavy converter.

ine not; condensed in 3l; gov h 32, ehm-'With `the similfar aluminum chlord, oi or Ao1 l stable at about 600 f is employed, heating may be wholly byl the sensible heat ofjthe oil which then 1y^conta'in`- vapors of both saturated or unsaturatedlow boiling or light oils, may be passed 4 through 61' to 3l, which always contains aluminum chlorid vo'latilize'dffrom the The aluminum clilorid removes or satura-les the unsaturated vapors.

At any given 4stage in the operation the to repress any tendency to a rise in temperattire. 'An'djityis the object of -.the present invention to providenieans vfor yd'elivering a large amount of heat to the bath at about .this temperature without any -risk of local overheating. The reaction 'temperature is generally somewhere between 500 and 550 F.: and in. the presentinvention the oilbathed surfaces ofthe heating elementscan be easily maintained at ory about this'ftemperature .with delivery of the required large volume of heat. ThetemV erature required inthe fluids circulating lt rough the heating elements to produce this temperature of course varies withl the speed of circulation,` the thickness ofthe metal wall, but in or. may indeed become unnecessary. converter.' In so' doing the amountofsatu.-

-Wliat weclairn is .-fl'- The process of eonverlingihgher boiL ing pret-roleu'm oilsinto lower boilingyoils which comprises establishing `and maintainv ing' a body ofsuch higher boilin` fpildand ui in aluminum chlorid, passing -heate heat transferring relationship but without contact` therewith in said body at a temper- -atnre sufiicient .to cause boiling` thereof, and

f ned.

libe irocess of converting higher boil-v ig tro eurn oils into lower boiling oils whici comprises establishing and maintaining ,a body of such higher boiling 'oil and V assin heated oil in heat transferring re ations rip but without Contact therewith insaid'body at a temperaondensing and collecting lower boiling oil ture sutlicient tri-cause boiling thereof, and condensing and collecting lower boiling oil formed. v 1 3.- Tlie process ofy converting higher boiling petroleum oils into lower boiling oils which -comprises establishing and maintaining a body of such higher boiling oil land aluminum chlorid, passing oil heated to a temperature sufficient. to produce vapors, lfrein-such heated oil in heat transferring.

relationship but withoutcontact therewith in said body at a ten'ipcraturer'sulcient to transferring relationshi a boilinnr thereof, condensing and co'l- `lecti'ng. lowernoiling `oil formed from said hotly, separating and* condensing :the'vapers ot4 said heating .oilI and. returning ythe 5 condcnsate ithcreot'vto thesaid b goingjtreatnient. l

4. The process of converting higher boiling vpetroleum oils.;int o lowervboiling oils f which com-prises 'establishing and rn ody underaintainloing'alhody 'of such higher boiling oil and f, l aluminum chlorid, passing heated oil .in heat. :transferring relationship but without con"- tact therewith in said body ,ata temperatme suliicient to causeboiling thereof;` condens-l boilingoill'formed'; allowing ja. portienfof .thef'lieatingoill to flash .into vapors outof contact with' the body ofoil after'said heating oil has passed through the heat transfer sta'geland se'par'ating and condensing such vapors.'-

5i Thefprocess of converting higher boilfing.v petroleum oils `into lowerl boiling oils .t Which-y cmprises establishing and maintaini1ig'5a.body `otsuchhigher-boiling oil and aluminum chlorid,-passingheatedoil. in heat p but 'without contacttherewith. in said body at. a temperature* sufIicien-t to/canse' boiling til1ereof,'icjondeiis-' 4ing and collecting lower .fboilingzxoil formed,v Q all-owing a portionv of the heating oil to flashv v into yapors ont yotfcontacty ywith the' body ot oil after said heating oil has passed through the heat transfer 'stageseparating and con-` :densing such vapors and returning the con.: densate thereot'to the said body` undergo'- ing treatment i c "f l G. The process of1-convertinghigher boil- .g ing petroleumpils into lower 'l'ioi'ling oilsvv f which comprises establishing and maintain- 'l ing a vbodyofisueh .higher boilingloil and aluminum clilorid` passing heated oil in heat transferring relationship but without con? tact therewith in said body at a temperature suiiicient to vcause boiling-thereof and production o'tvapors of lower boiling oil,'a11ow ing a. portion of the heating oil to flash into g lvapors. out of contact with the bodyf 'oil Lafter said heating oil has passed through thfef l heat transfer stage, separating and. their mixing such vapors with vapors of `"thev low' g A- boiling oilv from the'said body undergoing f. Itreatalwnt and `condensingthe mixetl vapors.

7.. The process of converting higher-boil- -,t-fingpetroleum oils into loftve'rboiling oils fvwhich' comprises establishing and maintain'- suiclent to cause bolllngtthereof..condensing. nd Vcollecting lower ho'lingfgp'ily"formedfl" :fig rlowirig'a portionofthe"heating oil toflash into vapors M after said heating oil has passed through the lheat transfer stage, separating and condens- 719.66 :if i

ing such vapors, and supplyixigesh oil to the lieating'system -to re'pla'e 'thefoil` va horizedv 8. TheA process of convertinghigher boiling petroleum:ols'into' lower "boiling oils which comprises establishingl andmaintain-- 'ing a body 'of such higher 'boilingoil and `=aluminumcliloridi passing heatedp'lin heat transferring' relationship but witliohtA contact therewith in; said body` at a temperature lSutiicie-nt to c a'nselioilingfthiwf 'and prodlctiorr of vaporsot lower boiling oil, con- -fdensing and 'colleetingf't'he lower boiling oil fm-ined,'allowing a portion of the heating oil tri-flash into `vapors after said oil'has passed through ltheheat 'transfer stage,"pa1tiall`y condensing 'these vapors, sending the 'condensate to the main body o f oil undergoing treatment and separately `condensing vthe remaining vapors.

"9.' The process of c ing f which comprises lestablishing and maintain- "in'g a b'ody of siich l1igl1er boili ngoil and aluminum chlric ,passing heated oil'in heat 'transferring relationship but rwithoutcon- 'tact therewith "in said' bodyat 'a .temperatu 1 production "of Vvapors of lower' boiling oil 'condensing and collecting the yloier boiling oil formed, allowing a portion ot thefheating oil `toil :passed through the'hea't. transfer stage, par- "tially condensingfthese Jfaiporsg'gsending the leondensate of the partially condel'ised "vapors to' thehiainbo y!'etoil"undergoing treat- `pleut and'l conde "tot said heating oil'witlr`tl1elower boiling oil vaporsV formed from saidbody. 1l `10.The process of yconverting,higher boilon ver-'ting higher boilwhich comprises establishing' and. maintain- 'hatedlto a leraeking 'temperature in ,heat transferring relationship but without 'conl'.actz`` therewith in"`said liodygniaintaining saidu body `at a tempeiatnre"sufficient tocause boilin thereofby suchpnssag'e of heated oil con ensing and Vcollecting vapors .of i lowen boiling oil Lfformed from said `body, separatin vthe va- 'pors formed inthe heating of sai oilgto-a cracking 'temperature and conde' `vapors.'

1.1. -The process of converting higlier-jboil# jing petroleumfpils into lowerboiling 011s *which comprises-establishing and maintainusing'the .remaining vapors f ing'petroleum oils into lower-boiling oils petroleum oils intolowerhoiling oils s re' siiiii'cie'iitto' cau'se'boiling thereof and ilashfinto vapors afterfv said f oil l has ingabndzy of such higher .boiling oil and;l

,ilingoil formed from Leonesa -said body, separating the vapors formed 'in the. heatlng of said oil to'- a crackin temperature, condensingsuch vapors an continuously supplying fresh oil to the heatlng system to replace thatremoved as vapors.

12. The process o f converting hivher boilv ingpetroleum oils into lower boiling oils whic comprises establishing and maintaining a body of such higher boiling' oil and aluminum chlorid, passing oil heated to 'a cracking temperature in heat transferring relationship but without lcontact 'therewith in said body, maintaining said' body at'a temperature suiicient to cause boilin ltheref of bysuch passage of lheated 011 rcon ensmg and ,collecting 'lower boiling oil ormed from'` said body, separating the vaporsA formed 1n.

the heating of said oil to a cracking temperature, partially condensin theseva ors, sending ,t e vcon `ensate to t 1e mam ody undergoing Ltreatment and separately condensin the remaining vapors.

13. fhe process `of converting higher boiling petroleum oils finto lower boiling voils Whichkcoxfnprises establishing l,and maintaining a body of such highei boiling oil and valuminum chlorid, passinrroil heated to aA vcracking temperature in llient transferring .relationshipgbut Without contact therewith in said body, maintaining said body atV a temperature sufficient to cause vboiling there-" ofy by such passage `of heated oil, condensing and collecting vapors oflower boiling oil formed from said body, separating the' vapors formed in the heating of saidjheating oil to a cracking' temperaturel and mixing these vapors with' vapors of the low boiling oils from the main body undergoing treatemnt and condensing vapors of 'the heating oll such body to a boiling temperature with the vapors of low boiling oil from said bodfj"`- Y l The process of converting higher boiling petroleum oils into lower boiling oils which comprises establishing and maintaining a bodyjf such higher boiling* oil in admixture ivith 'aluminum chlorid, heating ing heated oil in heat transfer relationship thereto but out of Contact therewith, thus by pass-l producing vapors of lower boiling oil and igher boiling oil in admixture with vaporized aluminum chlorid, permittin a part of the oil used for heating to flash into vapor I after the .said body -has been heated by said oil, conducting the vapors so flashed to the mixture Vof vaporized oil and chlorid, cooling said mixture to condense the said vapors of higher boilin oil, aluminum chlorid and a portion 'of tie flashed vapors, conducting the resultant condensate to the body undergoing treatment, and' condensing' said vapors of lower boiling oil together `With the remaining uncondensed portion'of the iiashed vapors.

' 15. The process of converting higher boil-` ing etroleum oils'intok lower boiling oils wluc 1 comprisesestablishing and maintainlng a body of such lugher boiling oil in admixture `with aluminum |chlorid, 'heating a separate mass of'oil tocracking temperature and passijngjthe same in heat transferring'.

renumis'lap were first said/italy bastare contact tlieneivith,` to liat'saigdffirst and A produce vapors f lower.' b ang oil and the chlorid, conducting the saidl clilorid afnd'vsaid bath ofv oil and chlorid at thetemperature A' of vfree ebullition and furnishing the heat units trequired by said ebullition by hot'oil in, peat-communicating relationship to said batirr A, testimony whereof, we have hereunto ailixed our signatures, this 3rd dayv of May,

, GEORGE L. PRICHARD.- v -vHERBERT HENDERSON. 

